Fábio Santos de Oliveira

A sensitive flow analysis system for the fluorimetric determination of low levels of formaldehyde in alcoholic beverages

A sensitive FIA method was developed for the selective determination of formaldehyde in alcoholic beverages. This method is based on the reaction of Fluoral-P (4-amine-3-pentene-2-one) with formaldehyde, leading to the formation of 3,5-diacetyl-1,4-dihydrolutidine (DDL), which fluoresces at lambda(ex)=410nm and lambda(em)=510nm. The analytical parameters were optimized by the response surface method using the Box-Behnken design. The proposed flow injection system allowed for the determination of up to 3.33x10(-5)molL(-1) of formaldehyde with R.S.D.<2.5% and a detection limit of 3.1ngmL(-1). The method was successfully applied to determine formaldehyde in alcoholic beverages, without requiring any sample pretreatment, and the results agreed with the reference at a 95% confidence level by paired t-test. In the optimized condition, the FIA system proved able to analyze up to 60 samples/h.

Spectrophotometric determination of sulphate in automotive fuel ethanol by sequential injection analysis using dimethylsulphonazo(III) reaction

A sensitive SIA method was developed for sulphate determination in automotive fuel ethanol. This method was based on the reaction of sulphate with barium-dimethylsulphonazo(III) leading to a decrease on the magnitude of analytical signal monitored at 665 nm. Alcohol fuel samples were previously burned up to avoid matrix effects for sulphate determinations. Binary sampling and stop-flow strategies were used to increase the sensitivity of the method. The optimization of analytical parameter was performed by response surface method using Box-Behnker and central composite designs. The proposed sequential flow procedure permits to determine up to 10.0mg SO(4)(2-)l(-1) with R.S.D. <2.5% and limit of detection of 0.27 mg l(-1). The method has been successfully applied for sulphate determination in automotive fuel alcohol and the results agreed with the reference volumetric method. In the optimized condition the SIA system carried out 27 samples per hour.

Multivariate optimization of a GC–MS method for determination of sixteen priority polycyclic aromatic hydrocarbons in environmental samples

This paper describes the development and optimization, by using multivariate analysis, of a GC-MS-SIM method for evaluation of the 16 polyaromatic hydrocarbons considered as priority pollutants in atmospheric particulate material by the US EPA. In order to assure an adequate separation in the shortest analysis time, a multivariate design was used to set the conditions of the oven temperature program. The optimization process was carried out using factorial fractional design and Box-Behnken design. The following factors were evaluated: initial temperature, temperature rate #1, intermediary temperature, temperature rate #2, and final temperature. The optimized conditions were set at: 70 degrees C (2 min) --> 200 degrees C (30 degrees C/min, 5 min) --> 300 degrees C (5 degrees C/min, 1.67 min). Moreover, we have also optimized the injector temperature as 310 degrees C and sampling time as 0.8 min. The total analysis time was 33 min. Validation of GC-MS-SIM yielded satisfactory results for repetitivity of the detector response and retention times, and linearity of calibration curves. LOD were established as 0.13-0.34 ng/mL (peak area) and 0.18-0.72 ng/mL (peak height). The method has been shown to be appropriate for the analysis of samples of atmospheric particulate material and/or other environmental matrices.

Determination of Total Aldehydes in Fuel Ethanol by MBTH Method - Sequential Injection Analysis

A sensitive SIA method was developed for total aldehyde determination in automotive fuel ethanol samples. It was based on the selective reaction of aliphatic aldehydes with 3-methyl-2-benzothiazolone hydrazone (MBTH) with the formation of blue dye in the presence of Fe3+. Monosegmentation and binary sampling were employed to increase the sensitivity of the method. In order accelerate reaction rate of MBTH and aldehyde a mixing coil was inserted into a microwave oven cavity were the sample zone was homogeneously heated. The linear range was 0.3-6 mg L-1 with a precision, expressed as relative standard deviation, lower than 2.5% and detection limit of 60 mg L-1. The method has been successfully applied to the determination of total aldehydes in fuel ethanol and the results agreed with those obtained with 2,4-DNPH-HPLC. In the optimal condition the system can carry out 10 samples per hour.

Reagent generation assisted by ultrasonic irradiation

In this work, the potential of reagent generation assisted by ultrasonic irradiation was evaluated for Cr(III) oxidation and arsine formation. Free radical formation by sonolysis of aqueous solutions was evaluated. The sonication of an aqueous solution saturated with CCl4 leads to chlorine radical formation while the irradiation of water in the presence of metallic zinc leads to hydrogen production. The low relative standard deviations of the proposed procedures indicate that the method can be applied for analytical purposes.

Volatile Organic Compounds Obtained by in Vitro Callus Cultivation of Plectranthus ornatus Codd. (Lamiaceae)

Plectranthus spp (Lamiaceae) are plants of economic importance because they are sources of aromatic essential oils and are also cultivated and several species of this genus are used as folk medicines. This paper describes the effects of different concentrations of the 2,4-dichlorophenoxyacetic acid (2,4-D) and 1-naphthaleneacetic acid (NAA) on the induction of callus from nodal segments of Plectranthus ornatus Codd and in the production of volatile organic compounds (monoterpenes and sesquiterpenes). The 20 and 40 day calli were subjected to solid phase micro extraction (HS-SPME) and submitted to GCMS analysis. Variations in VOCs between the samples were observed and, a direct relationship was observed between of the major constituent detected (α-terpinyl acetate) and the monoterpenes α-thujene, α-pinene, β-pinene, camphene, sabinene and α-limonene that were present in the volatile fractions. Besides α-terpinyl acetate, isobornyl acetate and α-limonene were also major constituents. Variations were observed in VOCs in the analyzed periods. The best cultivation media for the production of VOCs was found to be MS0 (control). Moderate success was achieved by treatment with 2.68 µM and 5:37 µM NAA (Group 2). With 2,4-D (9.0 µM), only the presence of α-terpinyl acetate and isocumene were detected and, with 2.26 µM of 2,4-D was produced mainly α-terpinyl acetate, α-thujene and β-caryophyllene (16.2%). The VOC profiles present in P. ornatus were interpreted using PCA and HCA. The results permitted us to determine the best cultivation media for VOC production and, the PCA and HCA analysis allowed us to recognize four groups among the different treatments from the compounds identified in this set of treatments.

A semi-continuous analyzer for the fluorimetric determination of atmospheric formaldehyde

This paper describes a sensitive and selective semi-continuous analyzer (FORMAL-FLU) for the fluorimetric determination of atmospheric formaldehyde. The method is based on the reaction between formaldehyde and Fluoral-P, producing the fluorescent derivative 3,5-diacetyl-1,4-dihydrolutidine (DDL) which, when excited at 410 nm, fluoresces at 510 nm. This analyzer consists of a gas diffusion chamber with a central microporous Teflon tube, with high gas permeability, filled with Fluoral-P solution. The air sample is pumped continually along the external tube and formaldehyde permeates the internal tube membrane, where it reacts selectively with Fluoral-P to form DDL. The analytical parameters of air sampling flow rate, sampling time interval and Fluoral-P reagent flow rate were optimized by the response surface method, using the Box-Behnken design. Under optimal conditions, air samples were pumped through the annular space of a gas diffusion chamber equipped with a central tube of microporous Teflon (17 cm long, 1.4 mm i.d., 2.15 mm e.d., 70% of porosity and 2 µm average pore diameter) filled with Fluoral-P at 2.5 mL min-1 for 30 min. After sampling, the mixture was directed at 1.3 mL min-1 to a 2.0 m long reaction coil immerged in a thermostatic bath at 80 oC to improve the sample/reagent mixture and reaction rate, then to the fluorimetric detector (λex = 410 nm λem = 510 nm), where the signal was acquired and recorded by an integrator. Peak heights were measured and these values were used in the calibration and determination steps. Under these conditions, the limit of detection was 0.55 ng mL-1 and the coefficient of variation was 8.6%. The main advantage of the FORMAL-FLU system is its selectivity for formaldehyde, without significant interference from bisulfite and other aldehydes, especially acetaldehyde, low blank level, resulting in low detection limits and, above all, using a single sampling and measuring device equipment which allows for in situ measurements.

Application of partial least squares calibration for multicomponents determination by flow injection–solid phase spectrophotometry

This article reports the use of solid phase spectrophotometry associated with flow injection technique for simultaneous determination of zinc and nickel with 1-(2-thiazolylazo)-2-naphthol (TAN) immobilized on a C18 bonded silica support in the concentration range from 0.30 to 1.0 μg mL −1 of both ions. The multicomponent analysis was implemented using the absorbance signals in different intervals of time in a flow injection analysis peak for each sample solution inserted into the analytical path. A partial least squares (PLS) algorithm for model construction was developed in QuickBasic 4.5 as a subrotine in order to assemble it in a data acquisition program, permitting the concentration estimation in real time. The proposed method was successfully applied to nickel and zinc determination in synthetic mixtures with analytical throughput of 43 samples per hour. The results obtained with the proposed method were compared with Inductively Coupled Plasma Atomic E Mission Spectrometry (ICP-AES) data, and the results agreed with 95% confidence level.

Emprego de padrão único para a construção de curvas analíticas em sistema de análise por injeção em fluxo associado à espectrofotometria em fase sólida

In this work two procedures were proposed for analytical curves construction using a single standard solution employing a flow injection system with solid phase spectrophotometric detection (FI-SPS). A flow cell contends the chromogenic reagent 1-(2-tiazolylazo)-2-naphtol was positioned on the optical path. The first procedure was based on controlled concentration of analyte on solid phase and the relations between absorbance and the total volume of injected allowed the calculation of analyte concentration. The second procedure was developed employing controlled dispersion/retention in flow system where analyte concentration was obtained by exploiting the relation between transient signals of samples and single standard solution at equivalent reading time. The procedures were successfully applied for zinc determination in synthetic solutions with good precision and accuracy at 95% confidence level.

Cadmium and lead retention in fresh and rotten red meat

The metal sorption capacity in fresh and rotten red meat was evaluated for Cd2+ and Pb2+ ions at pH 6 and the process involved in the studied metal retention was discussed. For the experimental set, an eight channels multi-port selection valve was employed to mechanise the sample preparation. The cadmium and lead concentrations were determined by ICP-OES. A high retention (> 80%, m/m) of Cd2+ and Pb2+ ions, in fresh and rotten bovine muscle was found, indicating the potential contamination risks related to the consumption of meat submitted to inappropriate conditions of abattoir, handling, storage and commercialisation. Seventy per cent of the cadmium was released with the immersion of meat in acetic acid at 1% (v/v), revealing that cookery practices may act on contaminant sorptive processes in meat structure.